JP5693108B2 - Phosphor, method for manufacturing the same, and light emitting device having the same - Google Patents
Phosphor, method for manufacturing the same, and light emitting device having the same Download PDFInfo
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- JP5693108B2 JP5693108B2 JP2010203248A JP2010203248A JP5693108B2 JP 5693108 B2 JP5693108 B2 JP 5693108B2 JP 2010203248 A JP2010203248 A JP 2010203248A JP 2010203248 A JP2010203248 A JP 2010203248A JP 5693108 B2 JP5693108 B2 JP 5693108B2
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 96
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000000034 method Methods 0.000 title description 5
- 239000013078 crystal Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000005284 excitation Effects 0.000 description 17
- 239000000758 substrate Substances 0.000 description 10
- 239000011575 calcium Substances 0.000 description 9
- 238000010304 firing Methods 0.000 description 9
- 229910052712 strontium Inorganic materials 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 229910052788 barium Inorganic materials 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000009877 rendering Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 229910052771 Terbium Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000003991 Rietveld refinement Methods 0.000 description 3
- 229910052775 Thulium Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000005424 photoluminescence Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 101100476480 Mus musculus S100a8 gene Proteins 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000000547 structure data Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000012856 weighed raw material Substances 0.000 description 1
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Description
本発明は、蛍光体や、その製造方法及びこれを用いた発光装置に関し、より詳しくは、青緑色蛍光体、その製造方法及びこれを用いた発光装置に関する。 The present invention relates to a phosphor, a manufacturing method thereof, and a light emitting device using the same, and more particularly to a blue-green phosphor, a manufacturing method thereof, and a light emitting device using the same.
青色発光ダイオード（ＬＥＤ）や青色レーザー（ＬＤ）等を励起源とし、これを受けて蛍光を発光させ、白色光を発光させる発光装置が、従来の蛍光灯等と比較して消費電力が低く長寿命であることから、種々利用されている。また、これらのＬＥＤを用いた発光装置は、不要な紫外線や赤外線を含まない光が簡単に得られるため、紫外線に敏感な文化財や芸術作品、熱照射を嫌う物等の各種照明等にも好適である。かかる発光装置の蛍光体として、ＬＥＤによる発光効率がよく、ＬＥＤによる劣化が少ない（Ｙ，Ｇｄ）3（Ａｌ，Ｇａ）5Ｏ12：Ｃｅ3+等のいわゆるＹＡＧ：Ｃｅ系蛍光体が使用されている。この種の発光装置として、具体的には、例えば、（ＲＥ1-xＳｍx）3（ＡｌyＧａ1-y）5Ｏ12：Ｃｅで表され、式中、ＲＥは、Ｙ、Ｇｄから選択される少なくとも１種で青色ＬＥＤにより励起され黄緑色を発光する蛍光体をモールドした発光ダイオード等が報告されている。しかしながら、これらの発光ダイオードにおいては、青色と黄色の補色による白色であることから、充分な演色性が得られないという問題がある。 A light-emitting device that emits white light using a blue light-emitting diode (LED) or blue laser (LD) as an excitation source is low in power consumption and long compared with conventional fluorescent lamps. Since it has a long life, it is used in various ways. In addition, light-emitting devices using these LEDs can easily obtain light that does not contain unnecessary ultraviolet rays and infrared rays, so they can be used for various illuminations such as cultural assets and art works sensitive to ultraviolet rays, and objects that do not like heat irradiation. Is preferred. As a phosphor of such a light-emitting device, a so-called YAG: Ce-based phosphor such as (Y, Gd) 3 (Al, Ga) 5 O 12 : Ce 3+ is used which has good luminous efficiency by the LED and little deterioration by the LED. ing. As this type of light emitting device, specifically, for example, (RE 1-x Sm x ) 3 (Al y Ga 1-y) 5 O 12: represented by Ce, wherein, RE is, Y, from Gd There has been reported a light emitting diode or the like in which a phosphor that is excited by a blue LED and emits yellowish green is molded with at least one selected. However, these light emitting diodes have a problem that a sufficient color rendering property cannot be obtained because they are white by complementary colors of blue and yellow.
このような発光装置における演色性を向上させるため、青色ＬＥＤの発光により青緑色から緑色の蛍光を発光するオキシ窒化物蛍光体が開発されている（特許文献１−３）。ＬＥＤやＬＤからの青色により励起され、更なる発光効率の向上を図ることができる高強度の青緑色の蛍光を発光する蛍光体や、これを用いた発光装置が要請されている。 In order to improve the color rendering in such a light emitting device, an oxynitride phosphor that emits blue-green to green fluorescence by light emission of a blue LED has been developed (Patent Documents 1-3). There is a demand for a phosphor that emits high-intensity blue-green fluorescence that can be excited by blue from an LED or LD and can further improve luminous efficiency, and a light-emitting device using the phosphor.
本発明の課題は、充分なバンドギャップを有し、ＬＥＤやＬＤから発光される青色により励起され、高強度な青緑色の蛍光を発光することが可能な蛍光体を提供し、更に、この蛍光体を容易に効率よく製造することができる製造方法を提供することにある。 An object of the present invention is to provide a phosphor that has a sufficient band gap, is excited by blue light emitted from an LED or LD, and can emit high-intensity blue-green fluorescence. An object of the present invention is to provide a production method capable of producing a body easily and efficiently.
また、本発明は、励起光とするＬＥＤやＬＤからの青色との演色性に優れ、色調に優れた白色光を得ることができ、且つ、発光効率がよく、充分な発光強度を有し、消費電力の低減を図ることができ、照明用として好適な蛍光体やその製造方法を提供し、これを用いた発光装置を提供することにある。 In addition, the present invention is excellent in color rendering with blue from LED or LD as excitation light, can obtain white light with excellent color tone, has good luminous efficiency, and has sufficient luminous intensity, An object of the present invention is to provide a phosphor that can reduce power consumption and is suitable for illumination and a method for manufacturing the same, and to provide a light-emitting device using the phosphor.
本発明者らは、ＬＥＤやＬＤから発光される青色光のエネルギーとその励起エネルギーが近似し、充分なバンドギャップを有し、しかも、励起により発光される蛍光波長が青緑色系である蛍光体を見い出すべく鋭意研究を行った。その結果、特定の元素組成の蛍光体が、ＬＥＤやＬＤから発光される紫外光から青色光により発光ピーク強度が高い青緑色の蛍光を発光することの知見を得た。かかる知見に基づき本発明を完成するに至った。 The present inventors have obtained a phosphor whose blue light energy emitted from an LED or LD approximates its excitation energy, has a sufficient band gap, and has a blue-green fluorescence wavelength emitted by excitation. We conducted intensive research to find out. As a result, it has been found that a phosphor having a specific element composition emits blue-green fluorescence having a high emission peak intensity due to blue light from ultraviolet light emitted from an LED or LD. Based on this finding, the present invention has been completed.
すなわち本発明は、 組成式（１）
Ｃａ ７−ｙ Ｅｕ ｙ Ｓｉ １０ Ｏ ６ Ｎ １４ （１）
（式中、ｙは０．０１３≦ｙ≦０．０１５を満たす。）で表され、格子定数ａ（ｎｍ）が１．５＜ａ＜１．６を満たす立方晶系で空間群Ｐａ−３（Ｎｏ．２０５）の結晶構造を有することを特徴とする蛍光体を提供する。
That is, the present invention provides a composition formula (1)
Ca 7-y Eu y Si 10 O 6 N 14 (1)
( Wherein y satisfies 0.013 ≦ y ≦ 0.015 ) and the space constant Pa-3 is a cubic system in which the lattice constant a (nm) satisfies 1.5 <a <1.6. A phosphor having the crystal structure of (No. 205) is provided .
また、本発明は、上記蛍光体の製造方法であって、組成式（１）を構成する元素を含む化合物を、陽圧下で焼成することを特徴とする蛍光体の製造方法に関する。 The present invention also relates to a method for producing a phosphor, characterized in that a compound containing an element constituting the composition formula (1) is baked under a positive pressure.
また、本発明は、上記蛍光体を用いたことを特徴とする発光装置に関する。 The present invention also relates to a light-emitting device using the phosphor.
本発明の蛍光体は、充分なバンドギャップを有し、ＬＥＤやＬＤから発光される青色により励起され、高強度な青緑色の蛍光を発光することができる。 The phosphor of the present invention has a sufficient band gap, and is excited by blue light emitted from an LED or LD, and can emit high-intensity blue-green fluorescence.
また、本発明の蛍光体の製造方法は、上記蛍光体を容易に効率よく製造することができる。 In addition, the phosphor production method of the present invention can produce the phosphor easily and efficiently.
また、本発明の発光装置は、励起光とするＬＥＤやＬＤからの青色との演色性に優れ、色調に優れた白色光を得ることができ、且つ、発光効率がよく、充分な発光強度を有し、消費電力の低減を図ることができ、照明用として好適である。 In addition, the light emitting device of the present invention is excellent in color rendering with blue light from LEDs and LDs as excitation light, can obtain white light with excellent color tone, has high luminous efficiency, and has sufficient luminous intensity. And can reduce power consumption and is suitable for illumination.
本発明の蛍光体は組成式（１）
ＡxＬyＳｉzＯbＮc （１）
（式中、Ａは少なくともＣａを含み、Ｂａ、Ｓｒ、Ｍｇ又はＺｎのいずれか１種又は２種以上を含んでいてもよい元素を示し、Ｌは少なくともＥｕを含み、Ｃｅ、Ｐｒ、Ｙｂ、Ｔｍ、Ｔｂ又はＳｍのいずれか１種又は２種以上を含んでいてもよい元素を示し、ｘは５．８≦ｘ≦７．８、ｙは０．００１＜ｙ≦０．２、ｚは６≦ｚ≦１０、ｂは６≦ｂ≦８、ｃは９≦ｃ≦１４を満たす数値を示す。）で表され、格子定数ａ（ｎｍ）が１．４５＜ａ＜１．６５を満たす立方晶系の結晶構造を有することを特徴とする。
The phosphor of the present invention has a composition formula (1)
A x L y Si z O b N c (1)
(In the formula, A represents an element that contains at least Ca, and may contain any one or more of Ba, Sr, Mg, or Zn, L contains at least Eu, Ce, Pr, Yb, An element that may contain one or more of Tm, Tb, or Sm is shown, x is 5.8 ≦ x ≦ 7.8, y is 0.001 <y ≦ 0.2, and z is 6 ≦ z ≦ 10, b is a numerical value satisfying 6 ≦ b ≦ 8, and c is a numerical value satisfying 9 ≦ c ≦ 14.) And the lattice constant a (nm) satisfies 1.45 <a <1.65. It has a cubic crystal structure.
本発明の蛍光体は、Ｃａ、Ｅｕ、Ｓｉ、Ｏ、Ｎを含み、必要に応じて、Ｂａ、Ｓｒ、Ｍｇ又はＺｎのいずれか１種又は２種を含んでいてもよく、或いは、Ｃｅ、Ｐｒ、Ｙｂ、Ｔｍ、Ｔｂ又はＳｍのいずれか１種又は２種以上を含んでいてもよい。式（１）中、Ｃａと、必要に応じて含有されるＢａ、Ｓｒ、Ｍｇ又はＺｎとの合計のモル比ｘは、５．８≦ｘ≦７．８を満たす。これらの元素のモル比ｘがこの範囲であることにより、式（１）で表される蛍光体の結晶構造が後述の立方晶系を有するものとなる。 The phosphor of the present invention contains Ca, Eu, Si, O, N, and may contain any one or two of Ba, Sr, Mg, or Zn as necessary, or Ce, Any one or more of Pr, Yb, Tm, Tb or Sm may be included. In formula (1), the total molar ratio x of Ca and Ba, Sr, Mg, or Zn contained as necessary satisfies 5.8 ≦ x ≦ 7.8. When the molar ratio x of these elements is in this range, the crystal structure of the phosphor represented by the formula (1) has a cubic system described later.
また、Ｅｕと、必要に応じて含有されるＣｅ、Ｐｒ、Ｙｂ、Ｔｍ、Ｔｂ又はＳｍとの合計のモル比ｙは、０．００１＜ｙ≦０．２を満たす。これらの元素のモル比ｙがこの範囲であることにより、式（１）で表される蛍光体の結晶構造が後述の立方晶系を有するものとなる。 Further, the total molar ratio y of Eu and Ce, Pr, Yb, Tm, Tb or Sm contained as necessary satisfies 0.001 <y ≦ 0.2. When the molar ratio y of these elements is within this range, the crystal structure of the phosphor represented by the formula (1) has a cubic system described later.
また、ケイ素原子のモル比ｚは６≦ｚ≦１０、酸素原子のモル比ｂは６≦ｂ≦８、窒素原子のモル比ｃは９≦ｃ≦１４を満たす。これらの原子のモル比がこの範囲であれば、式（１）で表される蛍光体の結晶構造が後述の立方晶系を有するものとなる。 Further, the molar ratio z of silicon atoms satisfies 6 ≦ z ≦ 10, the molar ratio b of oxygen atoms satisfies 6 ≦ b ≦ 8, and the molar ratio c of nitrogen atoms satisfies 9 ≦ c ≦ 14. If the molar ratio of these atoms is within this range, the crystal structure of the phosphor represented by the formula (1) has a cubic system described later.
式（１）で表される蛍光体は格子定数ａ（ｎｍ）が１．４５＜ａ＜１．６５の立方晶系の結晶構造を有する。このような立方晶系を有することにより、青色光により励起され、青緑色の蛍光を効率よく発光し、結晶性に優れた蛍光体が得られ、かかる蛍光体においては、励起光による結晶格子欠損に起因するフォノンの生成を抑制し、蛍光の発光が阻害されるのを抑制させ得る。 The phosphor represented by the formula (1) has a cubic crystal structure with a lattice constant a (nm) of 1.45 <a <1.65. By having such a cubic system, a phosphor that is excited by blue light and emits blue-green fluorescence efficiently and has excellent crystallinity is obtained. In such a phosphor, crystal lattice defects due to excitation light are obtained. It is possible to suppress the generation of phonons due to the above, and to inhibit the emission of fluorescence.
上記組成式（１）で示される蛍光体は、組成式（２）
Ａ7-yＬyＳｉ10Ｏ6Ｎ14 （２）
（式中、Ａ、Ｌ、ｙはそれぞれ式（１）中に示すＡ、Ｌ、ｙと同じものを示す。）で表され、格子定数ａ（ｎｍ）が１．５＜ａ＜１．６を満たす立方晶系で空間群Ｐａ−３（Ｎｏ．２０５）の結晶構造を有する蛍光体が特に好ましい。式（２）で表される蛍光体は上記組成により、格子定数ａ（ｎｍ）が１．５＜ａ＜１．６の立方晶系で空間群Ｐａ−３（Ｎｏ．２０５）の結晶構造を有する。このような立方晶系を有することにより、青色光により励起され、青緑色の蛍光を効率よく発光し、結晶性に優れた蛍光体が得られ、かかる蛍光体においては、励起光による結晶格子欠損に起因するフォノンの生成を抑制し、蛍光の発光が阻害されるのを抑制させ得る。
The phosphor represented by the composition formula (1) is composed of the composition formula (2).
A 7-y Ly Si 10 O 6 N 14 (2)
(Wherein A, L, and y are the same as A, L, and y shown in Formula (1), respectively), and the lattice constant a (nm) is 1.5 <a <1.6. A phosphor having a cubic structure and a crystal structure of the space group Pa-3 (No. 205) is particularly preferable. The phosphor represented by the formula (2) has a cubic structure in which the lattice constant a (nm) is 1.5 <a <1.6 and has a crystal structure of the space group Pa-3 (No. 205) with the above composition. Have. By having such a cubic system, a phosphor that is excited by blue light and emits blue-green fluorescence efficiently and has excellent crystallinity is obtained. In such a phosphor, crystal lattice defects due to excitation light are obtained. It is possible to suppress the generation of phonons due to the above, and to inhibit the emission of fluorescence.
結晶構造は粉末Ｘ線回折測定（ＲＩＮＴ−２０００；理学電機（株）製）により、Ｘ線回折パターン１０°〜１３０°の範囲で測定した。得られる回折パターンより抽出された回折ピークから結晶系を決定し、構造計算プログラムにより、最適化された格子定数の数値を得た。図１に示すように、式（１）で示される蛍光体は、３１．６度、３２．７度、３３．７度に回折ピークを有する。 The crystal structure was measured by powder X-ray diffraction measurement (RINT-2000; manufactured by Rigaku Corporation) in an X-ray diffraction pattern range of 10 ° to 130 °. A crystal system was determined from a diffraction peak extracted from the obtained diffraction pattern, and an optimized lattice constant value was obtained by a structure calculation program. As shown in FIG. 1, the phosphor represented by the formula (1) has diffraction peaks at 31.6 degrees, 32.7 degrees, and 33.7 degrees.
このX線回折パターンより未知構造解析およびリートベルト解析により、図７に示すようなリートベルト解析によりフィッティングされた回折パターンが得られる。フィッティングパラメータR値（Rwp、Rp、RB、RF）はすべて5%以下を示しており、求められた結晶構造が妥当であることを示している。構造解析の結果、結晶系は立方晶で空間群Pa-3（No.205）、単位格子は約1.548nmと見積もられ、図８に示すような具体的な結晶構造を得る。この結晶構造は、Siサイトはすべて[Si(O,N)4]多面体構造で構成されており、この母体結晶は共有結合性が強く、強固であり、熱的に安定であると推測することができる。図７および図８より得られたＣａ6.988Ｅｕ0.012Ｓｉ10Ｏ6Ｎ14の結晶構造データを表1に示す。 From this X-ray diffraction pattern, a diffraction pattern fitted by Rietveld analysis as shown in FIG. 7 is obtained by unknown structure analysis and Rietveld analysis. The fitting parameter R values (Rwp, Rp, RB, RF) all indicate 5% or less, indicating that the obtained crystal structure is appropriate. As a result of structural analysis, it is estimated that the crystal system is cubic, the space group Pa-3 (No. 205), and the unit cell is about 1.548 nm, and a specific crystal structure as shown in FIG. 8 is obtained. As for this crystal structure, all Si sites are composed of [Si (O, N) 4] polyhedral structure, and it is assumed that this base crystal has strong covalent bond, is strong, and is thermally stable. Can do. Table 1 shows the crystal structure data of Ca 6.988 Eu 0.012 Si 10 O 6 N 14 obtained from FIG. 7 and FIG.
式（１）、式（２）で表される蛍光体は、波長３００〜５００ｎｍによって励起されるワイドバンドギャップを有する。かかる励起エネルギーを有する励起光を発光する励起源として、青色レーザーや青色ＬＥＤ等を挙げることができる。上記励起源の青色ＬＥＤとしては、具体的には、ＩｎＧａＮ等を挙げることができる。 The phosphors represented by the formulas (1) and (2) have a wide band gap excited by a wavelength of 300 to 500 nm. Examples of an excitation source that emits excitation light having such excitation energy include a blue laser and a blue LED. Specific examples of the blue LED as the excitation source include InGaN.
上記蛍光体は上記ＬＥＤやＬＤ等から発光される青色により励起され、４５０〜６００ｎｍ波長の青緑色の蛍光を発光する。 The phosphor is excited by blue light emitted from the LED or LD, and emits blue-green fluorescence having a wavelength of 450 to 600 nm.
上記蛍光体を製造するには、目的とする元素組成に相当するように、各元素を含有する化合物を組み合わせ、陽圧下で焼成する方法を挙げることができる。原料として、蛍光体に含まれる元素の酸化物や窒化物を用いることができる。具体的には、酸化カルシウム、酸化バリウム、酸化ストロンチウム、酸化マグネシウム、酸化亜鉛、酸化ユウロピウム、酸化ケイ素、窒化ケイ素等を用いることができる。更に、結晶性の優れた構造の蛍光体を形成するため、結晶構造中の欠陥を少なくするためにフラックス材を用いてもよい。 In order to produce the phosphor, there can be mentioned a method in which compounds containing respective elements are combined and fired under a positive pressure so as to correspond to the target elemental composition. As a raw material, an oxide or nitride of an element contained in the phosphor can be used. Specifically, calcium oxide, barium oxide, strontium oxide, magnesium oxide, zinc oxide, europium oxide, silicon oxide, silicon nitride, or the like can be used. Further, in order to form a phosphor having a structure with excellent crystallinity, a flux material may be used to reduce defects in the crystal structure.
これら各原料を目的とする組成式に従って秤量、採取し、乾式または湿式で十分混合する。湿式混合の場合は、エタノールやイソプロピルアルコール等のアルコール、アセトン等の有機溶剤を用いることが好ましい。これらの有機溶剤と、秤量した原料を、セラミックス製等のボールミルにアルミナ若しくはジルコニア製などのボールと共に入れ、１時間から２４時間混合することができる。その後、有機溶剤を乾燥除去し、混合された原料粉末とすることができる。 These raw materials are weighed and collected in accordance with the target composition formula, and thoroughly mixed in a dry or wet manner. In the case of wet mixing, it is preferable to use an alcohol such as ethanol or isopropyl alcohol, or an organic solvent such as acetone. These organic solvents and the weighed raw materials can be put in a ball mill made of ceramics together with balls made of alumina or zirconia and mixed for 1 to 24 hours. Thereafter, the organic solvent can be removed by drying to obtain a mixed raw material powder.
得られた混合原料粉末をカーボンルツボやカーボントレイ、窒化ホウ素ルツボ、窒化ホウ素トレイなどの耐熱容器に充填し焼成する。焼成温度は、例えば、１３００〜１７００℃が好ましく、より好ましくは１４００〜１６００℃である。焼成時間は、例えば、１〜１０時間等とすることができる。上記焼成時の雰囲気としては、窒素ガスや、窒素と水素の混合ガス、アンモニア等還元雰囲気が好ましく、特に、窒素ガスであることが好ましい。 The obtained mixed raw material powder is filled in a heat-resistant container such as a carbon crucible, a carbon tray, a boron nitride crucible, or a boron nitride tray and fired. The firing temperature is, for example, preferably 1300 to 1700 ° C, more preferably 1400 to 1600 ° C. The firing time can be, for example, 1 to 10 hours. As the atmosphere at the time of firing, nitrogen gas, a mixed gas of nitrogen and hydrogen, a reducing atmosphere such as ammonia is preferable, and nitrogen gas is particularly preferable.
上記混合原料粉末の焼成雰囲気は陽圧とする。陽圧下で焼成することにより、Ｓｉ3Ｎ4等の窒化物が分解するのを抑制し、目的とする組成の蛍光体を得ることができる。かかる焼成雰囲気の圧力としては、０．８〜１．５０気圧等を挙げることができ、より好ましくは０．８５〜１．１気圧等である。焼成時の圧力が上記範囲であれば、粉末化の際に負荷する外力により結晶を破壊して蛍光体の発光効率を低下させるのを抑制することができる。焼成は、焼成後、冷却し、再焼成することを反復し、複数回に亘って行うこともできる。得られた焼成物に対し、粉砕、洗浄、乾燥、篩い分け等を施して、粉末状の蛍光体とすると、ＬＥＤ素子等に好適である。 The firing atmosphere of the mixed raw material powder is a positive pressure. By firing under a positive pressure, it is possible to suppress decomposition of nitrides such as Si 3 N 4 and obtain a phosphor having a desired composition. Examples of the pressure of the firing atmosphere include 0.8 to 1.50 atm, and more preferably 0.85 to 1.1 atm. If the pressure at the time of baking is the said range, it can suppress that the crystal | crystallization is destroyed by the external force loaded in the case of pulverization, and the luminous efficiency of fluorescent substance is reduced. Firing can be performed multiple times by repeating cooling and refiring after firing. The obtained fired product is pulverized, washed, dried, sieved, and the like to obtain a powdered phosphor, which is suitable for an LED element or the like.
本発明の発光装置は、上記蛍光体を用いたものであれば、いずれであってもよい。例えば、本発明の発装置としては、３００〜５００ｎｍの波長光を発光する半導体を有する発光ダイオード等のＬＥＤ素子や、エレクトロルミネッセンス素子、カソードからの電子を蛍光体へ直接衝突させ発光させる電界放出型表示（ＦＥＤ）や、真空蛍光表示（ＶＦＤ）等の電子線発光装置、その他冷陰極蛍光ランプや熱陰極蛍光ランプ等の蛍光ランプ等を挙げることができる。 The light emitting device of the present invention may be any as long as it uses the above phosphor. For example, as a light emitting device of the present invention, an LED element such as a light emitting diode having a semiconductor that emits light having a wavelength of 300 to 500 nm, an electroluminescence element, or a field emission type that emits light by directly colliding electrons from a cathode with a phosphor. Examples thereof include electron beam light emitting devices such as display (FED) and vacuum fluorescent display (VFD), and other fluorescent lamps such as cold cathode fluorescent lamps and hot cathode fluorescent lamps.
本発明の発光装置の一例として、図２の概略構成図に示すＬＥＤ素子を挙げることができる。図２に示すＬＥＤ素子には、主として、リフレクタの機能を有する筐体１２と、該筐体に固定されたサブマウント（図示せず）上に固定されたＬＥＤチップ１３と、該ＬＥＤチップ１３を包囲する透明樹脂１４と、透明樹脂を覆うように、例えば、ガラス製等の蛍光体含有シート１１とが設けられる。ＬＥＤチップ１３は、Ａｌ2Ｏ3またはＳＩＯの基板上にＧａＮ等の半導体等が積層されて形成される発光層を有し、該発光層が３００〜５００ｎｍの紫外光から青色光を発光するものが好ましい。ＬＥＤチップのＬＥＤは配線１５によりその電極がワイヤボンドされて図示しない電源に電気的に接続される。上記透明樹脂はＬＥＤチップの保護のため設けられ、ＬＥＤからの発光の透過性に優れ、そのエネルギーに対して耐性を有する、例えば、エポキシ樹脂、ユリア樹脂、シリコーン樹脂等が好適に用いられる。透明樹脂の上面に設けられる蛍光体含有シート１１には式（１）で表される蛍光体が含有される。シート１１には、ＬＥＤ素子から発光させる光を所望の波長にする場合、また、更なる演色性を得る場合には、必要に応じて、緑色、黄色、赤色などの蛍光を発光する蛍光体を含有させることができる。例えば、緑色発光蛍光体としては、Ｙ3（Ａｌ，Ｇａ）5Ｏ12：Ｃｅ、ＳｒＧａ2Ｓ4：Ｅｕ、（Ｂａ，Ｓｒ）2ＳｉＯ4：Ｅｕ、Ｃａ3Ｓｃ2Ｓｉ3Ｏ12：Ｃｅ、ＣａＳｃ2Ｏ4：Ｃｅ、Ｅｕ賦活β-サイアロン、（Ｓｒ，Ｂａ）Ｓｉ2Ｏ2Ｎ2：Ｅｕ、Ｂａ3Ｓｉ6Ｏ12Ｎ2：Ｅｕ、ＢＡＭ：Ｅｕ，Ｍｎ等を挙げることができる。黄色蛍光体としては、（Ｙ，Ｇｄ）3Ａｌ5Ｏ12：Ｃｅ、Ｔｂ3Ａｌ5Ｏ12；Ｃｅ、ＣａＧａ2Ｓ4：Ｅｕ、（Ｓｒ，Ｃａ，Ｂａ）2ＳｉＯ4：Ｅｕ、Ｅｕ賦活Ｃａ-α-サイアロン、Ｌａ3Ｓｉ6Ｎ11：Ｃｅ等を挙げることができる。赤色蛍光体としては、（Ｓｒ，Ｃａ）Ｓ：Ｅｕ、（Ｃａ，Ｓｒ）2Ｓｉ5Ｎ8：Ｅｕ、ＣａＡｌＳｉＮ3：Ｅｕ、（Ｓｒ，Ｂａ）3ＳｉＯ5：Ｅｕ、Ｋ2ＴｉＦ6：Ｍｎ等を挙げることができる。 As an example of the light emitting device of the present invention, an LED element shown in the schematic configuration diagram of FIG. 2 can be given. The LED element shown in FIG. 2 mainly includes a casing 12 having a reflector function, an LED chip 13 fixed on a submount (not shown) fixed to the casing, and the LED chip 13. For example, the surrounding transparent resin 14 and the phosphor-containing sheet 11 made of glass or the like are provided so as to cover the transparent resin. The LED chip 13 has a light emitting layer formed by laminating a semiconductor such as GaN on an Al 2 O 3 or SIO substrate, and the light emitting layer emits blue light from ultraviolet light of 300 to 500 nm. Is preferred. The LED of the LED chip is electrically connected to a power source (not shown) by wire-bonding its electrodes by wiring 15. For example, an epoxy resin, a urea resin, a silicone resin, or the like, which is provided for protecting the LED chip, has excellent light transmission from the LED, and has resistance to the energy, is preferably used. The phosphor-containing sheet 11 provided on the upper surface of the transparent resin contains the phosphor represented by the formula (1). The sheet 11 is provided with a phosphor that emits fluorescence such as green, yellow, red, etc., if necessary, when the light emitted from the LED element is set to a desired wavelength, or when further color rendering is obtained. It can be included. For example, as a green light emitting phosphor, Y 3 (Al, Ga) 5 O 12 : Ce, SrGa 2 S 4 : Eu, (Ba, Sr) 2 SiO 4 : Eu, Ca 3 Sc 2 Si 3 O 12 : Ce , CaSc 2 O 4 : Ce, Eu-activated β-sialon, (Sr, Ba) Si 2 O 2 N 2 : Eu, Ba 3 Si 6 O 12 N 2 : Eu, BAM: Eu, Mn, etc. . As the yellow phosphor, (Y, Gd) 3 Al 5 O 12 : Ce, Tb 3 Al 5 O 12 ; Ce, CaGa 2 S 4 : Eu, (Sr, Ca, Ba) 2 SiO 4 : Eu, Eu activation Examples thereof include Ca-α-sialon, La 3 Si 6 N 11 : Ce, and the like. As red phosphors, (Sr, Ca) S: Eu, (Ca, Sr) 2 Si 5 N 8 : Eu, CaAlSiN 3 : Eu, (Sr, Ba) 3 SiO 5 : Eu, K 2 TiF 6 : Mn Etc.
上記シートは、例えば、ガラス成分と蛍光体とを溶融混合して薄膜状に形成することができる。また、蛍光体は透明樹脂中に含有させることもできる。 For example, the sheet can be formed into a thin film by melting and mixing a glass component and a phosphor. Further, the phosphor can be contained in the transparent resin.
上記ＬＥＤ素子において、ＬＥＤから励起光が発光されると、シートに含有される蛍光体が励起され、青緑色領域を含んだ蛍光が発光される。これらの蛍光とＬＥＤからの青色光が、シート内で拡散され混色され、シート表面から色調の優れた白色光が放出される。 In the LED element, when excitation light is emitted from the LED, the phosphor contained in the sheet is excited, and fluorescence including a blue-green region is emitted. These fluorescent light and blue light from the LED are diffused and mixed in the sheet, and white light with excellent color tone is emitted from the sheet surface.
本発明の発光装置の一例として、電界放出型表示（フィールド・エミッション・ディスプレイ:ＦＥＤ）装置を例示することができる。この種のＦＥＤ装置としては、図３の部分略断面図に示すように、１対のガラス製等のアノード基板３１とカソード基板３２を備え、これらが図示しない支持枠により数ｍｍ以下の間隔で平行に配置され、内部が真空に保持されるようになっている。アノード基板３１には、内面に透明なアノード電極３１ａを介して蛍光体３１ｂが設けられ、蛍光体は赤色系蛍光体、青緑色系蛍光体、緑色系蛍光体等各画素が交互に付与されて形成される。これらの各蛍光体の各画素間にはこれらを隔離する黒色導電材からなる光吸収体が設けられていてもよい。青緑色系蛍光体として上記蛍光体が用いられ、これとの組み合わせにおいて、赤色系蛍光体、緑色系蛍光体が適宜選択される。一方、カソード基板３２の内面にはカソード電極３２ａを介して炭素膜等からなる電子放出素子（エミッタ）３２ｂが、各蛍光体の画素に対応して設けられる。各電子放出素子は支持枠に設けられる信号入力端子（図示せず）に接続されカソード基板に形成される図示しない配線によってそれぞれ電圧が印加されるようになっている。 As an example of the light emitting device of the present invention, a field emission display (field emission display: FED) device can be exemplified. As shown in the partial schematic cross-sectional view of FIG. 3, this type of FED apparatus includes a pair of glass-made anode substrate 31 and cathode substrate 32, which are separated by a support frame (not shown) at intervals of several millimeters or less. Arranged in parallel, the inside is kept in a vacuum. The anode substrate 31 is provided with a phosphor 31b on the inner surface through a transparent anode electrode 31a. The phosphor is provided with pixels such as a red phosphor, a blue-green phosphor, and a green phosphor alternately. It is formed. Between each pixel of each of these phosphors, a light absorber made of a black conductive material that separates them may be provided. The above phosphor is used as a blue-green phosphor, and a red phosphor and a green phosphor are appropriately selected in combination with the phosphor. On the other hand, an electron-emitting device (emitter) 32b made of a carbon film or the like is provided on the inner surface of the cathode substrate 32 via a cathode electrode 32a corresponding to each phosphor pixel. Each electron-emitting device is connected to a signal input terminal (not shown) provided on the support frame and is applied with a voltage by a wiring (not shown) formed on the cathode substrate.
このようなＦＥＤ装置において、カソード電極３２ａとアノード電極３１ａ間に電圧が印加されると、電子放出素子３２ｂから電子が放出され、放出された電子は矢印Ａに示すように、アノード電極３１ａに引き付けられ、蛍光体３１ｂに衝突し、蛍光を発生させ、発生した蛍光は白色光となってアノード基板３１から矢印Ｂに示すように、外部へ放出される。上記蛍光体を用いることにより、色調に優れた白色光を発光させることができる。 In such an FED device, when a voltage is applied between the cathode electrode 32a and the anode electrode 31a, electrons are emitted from the electron-emitting device 32b, and the emitted electrons are attracted to the anode electrode 31a as indicated by an arrow A. Then, it collides with the phosphor 31b to generate fluorescence, and the generated fluorescence becomes white light and is emitted from the anode substrate 31 to the outside as indicated by an arrow B. By using the phosphor, white light with excellent color tone can be emitted.
上記ＦＥＤ装置には、エミッタからの過剰な電子が放出され蛍光体表面を帯電させ、蛍光体と電子との衝突が阻害されるのを回避するため、蛍光体表面に電導層を設け、蛍光体表面に蓄積された電子とエミッタ間の異常放電を抑制するようにしてもよい。電導層は可視光領域で吸収がない透明な酸化インジウムや、酸化亜鉛等の導電性を有する微粒子を含有する電導性材料を蛍光体表面にコーティングする方法等により形成することができる。 The FED device is provided with a conductive layer on the phosphor surface in order to avoid excessive electrons from the emitter being emitted and charging the phosphor surface to prevent collision between the phosphor and the electrons. You may make it suppress the abnormal discharge between the electron accumulate | stored on the surface and an emitter. The conductive layer can be formed by a method of coating a phosphor material with a conductive material containing transparent indium oxide that does not absorb in the visible light region or conductive fine particles such as zinc oxide.
また、本発明の発光装置の一例として、真空蛍光表示（バキューム・フルオロセント・ディスプレイ:ＶＦＤ）装置を例示することができる。この種のＶＦＤ装置としては、図４の部分略断面図に示すように、ガラス製等の基板４１上に設けられた各配線４２に絶縁体層４３に設けられたスルーホール４４を介してそれぞれ接続されるアノード４５が設けられ、各アノード上には蛍光体層４６ａ、４６ｂ、４６ｃが形成される。蛍光体層４６ａ、４６ｂ、４６ｃは、それぞれ赤色系蛍光体、青緑色系蛍光体、緑色系蛍光体等を含有して交互に設けられる。青緑色系蛍光体としては上記蛍光体が用いられ、これとの組み合わせにおいて、赤色系蛍光体、緑色系蛍光体を適宜選択することができる。この蛍光体層を覆うように、上方にグリッド４７が配置され、グリッド４７は基板上に設けられた図示しない端子に導通するように設けられる。更に、グリッドの上方にフィラメント状のカソード４８が基板両端に設けられた支持体に張架されて設けられ、これらが真空空間を形成する容器４９内に設けられる。また、蛍光体表面に電導層を設け、蛍光体表面の帯電を抑制し異常放電を抑制するようにしてもよい。電導層は上記ＦＥＤ装置における電導層と同様に形成することができる。 Further, as an example of the light emitting device of the present invention, a vacuum fluorescent display (vacuum fluorocent display: VFD) device can be exemplified. As this type of VFD device, as shown in the partial schematic cross-sectional view of FIG. 4, each wiring 42 provided on a substrate 41 made of glass or the like is respectively connected through a through hole 44 provided in an insulator layer 43. Connected anodes 45 are provided, and phosphor layers 46a, 46b, and 46c are formed on each anode. The phosphor layers 46a, 46b, and 46c are alternately provided with red phosphors, blue-green phosphors, green phosphors, and the like. As the blue-green phosphor, the above-described phosphor is used, and in combination therewith, a red phosphor and a green phosphor can be appropriately selected. A grid 47 is disposed above the phosphor layer so as to cover the phosphor layer, and the grid 47 is provided so as to be electrically connected to a terminal (not shown) provided on the substrate. Further, a filamentary cathode 48 is provided above the grid so as to be stretched on a support provided at both ends of the substrate, and these are provided in a container 49 that forms a vacuum space. Further, a conductive layer may be provided on the phosphor surface to suppress abnormal charging by suppressing charging of the phosphor surface. The conductive layer can be formed in the same manner as the conductive layer in the FED device.
このような真空蛍光表示装置においては、カソードからの電子を蛍光体に当てて蛍光体からの発光により表示を行い、環境温度、特に低温による発光強度の変動が少なく、上記蛍光体を含有することにより演色性を図り、一定の蛍光を継続して発生させることができる。 In such a vacuum fluorescent display device, display is performed by emitting light from the phosphor by applying electrons from the cathode to the phosphor, and there is little fluctuation in emission intensity due to environmental temperature, particularly low temperature, and the phosphor is contained. Thus, color rendering properties can be achieved and constant fluorescence can be continuously generated.
以下、本発明の蛍光体を実施例を挙げて更に詳細に説明する。
［実施例１］
粉末原料として、ＣａＣＯ3を３．０８ｇ、Ｓｉ3Ｎ4を１．９２ｇ、Ｅｕ2Ｏ3を０．０１ｇ秤量し、原料を混合した。混合物を窒化ホウ素ルツボに充填し、電気炉にセットし、０．９気圧の窒素還元雰囲気中において１５００℃で３時間焼成した。焼成後は徐冷して、得られた焼成物を粉砕混合、洗浄して、目的のＣａ7-yＥｕyＳｉ10Ｏ6Ｎ14（ｙ＝０．０１５）の蛍光体を得た。
Hereinafter, the phosphor of the present invention will be described in more detail with reference to examples.
[Example 1]
As powder raw materials, 3.08 g of CaCO 3 , 1.92 g of Si 3 N 4 and 0.01 g of Eu 2 O 3 were weighed and mixed. The mixture was filled in a boron nitride crucible, set in an electric furnace, and fired at 1500 ° C. for 3 hours in a nitrogen reducing atmosphere of 0.9 atm. After firing, the product was gradually cooled, and the obtained fired product was pulverized, mixed, and washed to obtain a target phosphor of Ca 7-y Eu y Si 10 O 6 N 14 (y = 0.015).
得られた蛍光体について、以下のように励起光（Photoluminescence Excitation:ＰＬＥ）測定、フォトルミネッセンス（Photoluminescence:ＰＬ）測定を行った。 About the obtained fluorescent substance, excitation light (Photoluminescence Excitation: PLE) measurement and photoluminescence (Photoluminescence: PL) measurement were performed as follows.
［ＰＬＥ測定］
得られた蛍光体について、蛍光分光光度計（ＲＦ−５３００ＰＣ：島津製作所製）により、大気中室温雰囲気下で、励起波長を変化させ、蛍光体の発光ピーク波長をモニターして測定を行った。蛍光体を励起可能な波長範囲は３３０ｎｍ近傍にピークを有し、３００〜５００ｎｍに及んだ。励起光波長に対するＰＬＥ強度（励起スペクトル）を図５中の点線で示す。
[PLE measurement]
The obtained phosphor was measured with a fluorescence spectrophotometer (RF-5300PC: manufactured by Shimadzu Corporation) by changing the excitation wavelength and monitoring the emission peak wavelength of the phosphor in the atmosphere at room temperature. The wavelength range in which the phosphor can be excited has a peak near 330 nm and extends from 300 to 500 nm. The PLE intensity (excitation spectrum) with respect to the excitation light wavelength is indicated by a dotted line in FIG.
［ＰＬ測定］
得られた蛍光体について、励起光として３６５ｎｍを用いて、蛍光分光光度計（ＲＦ−５３００ＰＣ：島津製作所製）により、大気中室温雰囲気下で行った。発光は４９０ｎｍ近傍にピークを有し、４５０〜６００ｎｍに及んだ。得られた蛍光体のＰＬ強度（発光スペクトル）を図５中の実線で示す。
[PL measurement]
About the obtained fluorescent substance, it carried out by the fluorescence spectrophotometer (RF-5300PC: Shimadzu Corp. make) using the 365 nm as excitation light in air | atmosphere at room temperature atmosphere. The emission had a peak in the vicinity of 490 nm and ranged from 450 to 600 nm. The PL intensity (emission spectrum) of the obtained phosphor is shown by a solid line in FIG.
［実施例２］
粉末原料として、ＣａＣＯ3を３．１６ｇ、Ｓｉ3Ｎ4を１．７３ｇ、Ｅｕ2Ｏ3を０．０１ｇ、ＳｉＯ2を０．１１ｇ秤量して用いた他は、実施例１と同様にして蛍光体を作製し、目的のＣａ7-yＥｕyＳｉ10Ｏ6Ｎ14（ｙ＝０．０１３）の蛍光体を得た。得られた蛍光体について、ＰＬＥ測定、ＰＬ測定を行った。ＰＬＥ強度を点線で、ＰＬ強度を実線で、図６に示す。
[Example 2]
The same procedure as in Example 1 was conducted except that 3.16 g of CaCO 3 , 1.73 g of Si 3 N 4 , 0.01 g of Eu 2 O 3 and 0.11 g of SiO 2 were weighed and used as powder raw materials. A phosphor was produced, and the target phosphor of Ca 7-y Eu y Si 10 O 6 N 14 (y = 0.003) was obtained. About the obtained fluorescent substance, PLE measurement and PL measurement were performed. FIG. 6 shows the PLE intensity as a dotted line and the PL intensity as a solid line.
４６ａ、４６ｂ、４６ｃ 蛍光体層
１１ａ、３１ｂ 蛍光体
46a, 46b, 46c phosphor layers 11a, 31b phosphor
Claims (5)
Ｃａ ７−ｙ Ｅｕ ｙ Ｓｉ １０ Ｏ ６ Ｎ １４ （１）
（式中、ｙは０．０１３≦ｙ≦０．０１５を満たす。）で表され、格子定数ａ（ｎｍ）が１．５＜ａ＜１．６を満たす立方晶系で空間群Ｐａ−３（Ｎｏ．２０５）の結晶構造を有することを特徴とする蛍光体。 Composition formula (1)
Ca 7-y Eu y Si 10 O 6 N 14 (1)
(Wherein, y satisfies. The 0.013 ≦ y ≦ 0.015) is represented by space group with standing orthorhombic system satisfying the lattice constant a (nm) is 1.5 <a <1.6 Pa- A phosphor having a crystal structure of No. 3 (No. 205) .
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